EP0767163A1 - Procédé d'estérification de l'acide (méth)acrylique avec un alcanol - Google Patents
Procédé d'estérification de l'acide (méth)acrylique avec un alcanol Download PDFInfo
- Publication number
- EP0767163A1 EP0767163A1 EP96115453A EP96115453A EP0767163A1 EP 0767163 A1 EP0767163 A1 EP 0767163A1 EP 96115453 A EP96115453 A EP 96115453A EP 96115453 A EP96115453 A EP 96115453A EP 0767163 A1 EP0767163 A1 EP 0767163A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- bottom product
- esterification
- weight
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
Definitions
- the invention relates to a process for the esterification of (meth) acrylic acid with an alkanol in the presence of an esterification catalyst, in which unreacted starting compounds and the (meth) acrylic acid ester to be formed are separated off by distillation and an oxyester-containing bottom product is formed.
- (meth) acrylic acid denotes in a known manner acrylic or methacrylic acid.
- Oxyester formation is of particular importance in the production of acrylates of the C 1 to C 8 alkanols, in particular the C 4 to C 8 alkanols, very particularly in the production of n-butyl acrylate and 2-ethylhexyl acrylate.
- Any esterification reaction mixture is usually worked up in such a way that unreacted starting compounds and the Target esters are separated from the reaction mixture by distillation, the acid catalyst used for the esterification optionally being separated beforehand by extraction using water and / or aqueous alkali (cf., for example, Ullmann's Encyclopedia of Industrial Chemistry, Vol. A1, 5th Ed., VCH, pp. 167ff) .
- the bottom product remaining in the course of such a work-up by distillation contains the oxyesters, which cause a considerable loss in yield.
- JP-A-82/62229 describes the alkaline saponification of the high-boiling esterification residue. In this way, part of the alcohol used and acrylic acid and ⁇ -hydroxypropionic acid or their salts are obtained. A simple and economical recycling of the products into the esterification reaction is therefore not possible.
- JP-AS-72/15936 describes the production of acrylic esters by reacting ⁇ -alkoxypropionic acid esters with acrylic acid in the presence of strong acids (transesterification). As a by-product, however, equimolar amounts of ⁇ -alkoxypropionic acid are obtained which cannot be returned to the esterification reaction and therefore represent waste.
- the turnover is also low ( ⁇ 60%) and large amounts of titanate are necessary. This process is therefore uneconomical and pollutes the environment because of the large amounts of titanate to be disposed of.
- GB 923 595 is the extraction of monomers from the residue of the esterification of acrylic acid with alkanols in the absence of molecular Oxygen described.
- the removal of all volatile monomers before cleavage, the cleavage in the presence of sulfuric acid and the removal of the cleavage products with the aid of an inert gas stream are recommended.
- the cleavage is always at min. 300 ° C carried out.
- the residue is coke (17-40%). This must be "mined" removed from the reactor. Therefore, this process is neither economically nor on an industrial scale.
- Another disadvantage is the need to exclude oxygen.
- CN-A 1,063,678 describes the cleavage of the alkoxypropionic acid ester contained in the esterification residue in the presence of sulfuric acid in a cascade, the temperature and catalyst concentration (0.8 to 1.5%) being different in each reactor. Coupled with the cleavage is a distillation to separate alkanol and acrylate. The process is very cumbersome and does not achieve high sales.
- CN-A 105 8390 describes the splitting of alkoxypropionic acid esters in the presence of sulfuric acid etc. into alkanols and acrylic acid esters. This is done step by step. The cleavage is first carried out under reflux and then the reaction products are distilled off. The cleavage of the acrylic acid-containing ester residues from the ethyl / methyl acrylate production (ethyl ethoxypropionate, methyl methoxypropionate) is carried out in the presence of ethanol or methanol. Here, too, the process is complicated and does not achieve high sales.
- the invention has for its object to carry out the cleavage of the oxyesters contained in this bottom product and the further use of the resulting starting acid, starting alcohol and target ester in the course of the esterification without the disadvantages of the methods according to the prior art.
- the bottom product is separated off and the oxyesters contained in it are heated to 150 to 250 ° C. in the presence of acid and the pressure is adjusted so that the cleavage products formed under the aforementioned conditions from the oxyesters contained in the bottom product evaporate.
- the method is carried out in the presence of molecular oxygen.
- acids for example mineral acids, such as sulfuric acid or phosphoric acid, and / or organic acids, such as alkyl or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid, are added to the bottom product.
- the total amount of acid then contained can be 1 to 20% by weight, preferably 5 to 15% by weight, based on the amounts of the bottom product.
- a stripping gas which preferably contains molecular oxygen, is passed through the bottom product as entrainer for the cleavage products. Air or mixtures of air with inert gas (e.g. nitrogen) are expediently used as the stripping gas.
- a simple heatable stirred reactor with double-wall heating or heating coil, or else a forced-circulation evaporator, for example a falling-film evaporator or flash evaporator, coupled with a residence time vessel, can be used for working up the oxyesters obtained in the esterification as bottom product.
- a rectification device placed on the cleaving apparatus for example a packed column, packing column or tray column, may be appropriate. This rectification device is generally operated in a stabilized manner with polymerization inhibitors (for example phenothiazine, hydroquinone monomethyl ether, etc.).
- the reaction is carried out, for example, in such a way that the bottom product to be cleaved is continuously removed from the work-up of the esterification mixture by distillation and fed to the cleavage reactor with the cleavage catalyst.
- the reaction can also be carried out batchwise.
- a semi-continuous reaction is also possible, in which the product to be cleaved is fed continuously to the cleavage reactor which contains the cleavage catalyst and the bottom product is only removed from the cleavage reactor in batches after the cleavage has ended.
- the cleavage products are continuously separated off by distillation.
- esters are prepared by the customary processes (see Ullmann's Encyclopedia of Industrial Chemistry, Volume A1, 5th Ed., VCH, p. 167ff).
- an entrainer eg cyclohexane or toluene
- the esterification can be depressurized, with overpressure or underpressure both continuously and discontinuously.
- a circulation reactor made of glass (volume: 1 l), heated with a heating plug, was filled with 40 g of p-toluenesulfonic acid and 500 g of an esterification residue from the production of n-butyl acrylate that had been freed from the acidic esterification catalyst.
- the rest consisted of polymers, oligomers and polymerization inhibitor (phenothiazine).
- the gap temperature was 195 ° C and the working pressure was 1 atm.
- the cleavage reactor was continuously fed with esterification residue during the cleavage.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19536191 | 1995-09-28 | ||
DE19536191A DE19536191A1 (de) | 1995-09-28 | 1995-09-28 | Verfahren zum Verestern von (Meth)acrylsäure mit einem Alkanol |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0767163A1 true EP0767163A1 (fr) | 1997-04-09 |
EP0767163B1 EP0767163B1 (fr) | 2001-01-10 |
Family
ID=7773495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96115453A Expired - Lifetime EP0767163B1 (fr) | 1995-09-28 | 1996-09-26 | Procédé d'estérification de l'acide (méth)acrylique avec un alcanol |
Country Status (12)
Country | Link |
---|---|
US (1) | US5910603A (fr) |
EP (1) | EP0767163B1 (fr) |
JP (2) | JPH09110791A (fr) |
KR (1) | KR100441360B1 (fr) |
CN (1) | CN1084325C (fr) |
CA (1) | CA2184197A1 (fr) |
CZ (1) | CZ270196A3 (fr) |
DE (2) | DE19536191A1 (fr) |
MX (1) | MX9604041A (fr) |
MY (1) | MY115846A (fr) |
SG (1) | SG83651A1 (fr) |
TW (1) | TW472039B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6512138B1 (en) | 1999-05-18 | 2003-01-28 | Basf Aktiengesellschaft | Preparation of (meth)acrylates |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19851984A1 (de) * | 1998-11-11 | 2000-05-18 | Basf Ag | Verfahren zum Verestern von (Meth)acrylsäure mit einem Alkanol |
CN1238329C (zh) | 1999-03-06 | 2006-01-25 | 巴斯福股份公司 | 生产丙烯酸的方法 |
DE10007213A1 (de) * | 2000-02-17 | 2001-08-23 | Basf Ag | Verfahren zur Herstellung von Estern alpha,beta-ungesättigter Carbonsäuren |
CN1318374C (zh) * | 2001-11-28 | 2007-05-30 | 三菱化学株式会社 | 制备(甲基)丙烯酸化合物的方法 |
CN1260201C (zh) | 2001-12-04 | 2006-06-21 | 三菱化学株式会社 | (甲基)丙烯酸类的制造方法 |
WO2004078679A2 (fr) * | 2003-02-28 | 2004-09-16 | Union Carbide Chemicals & Plastics Technology Corporation | Procede pour la conduite de reactions a equilibre limite |
WO2005007609A1 (fr) | 2003-07-11 | 2005-01-27 | Basf Aktiengesellschaft | Procede de separation thermique destine a la separation d'au moins un flux de substances enrichi en (meth)acrylmonomeres |
KR100714631B1 (ko) * | 2004-04-29 | 2007-05-07 | 주식회사 엘지화학 | 아크릴산의 회수 방법 |
KR101178239B1 (ko) * | 2008-11-19 | 2012-08-30 | 주식회사 엘지화학 | (메트)아크릴산 에스테르의 회수방법 |
KR101346370B1 (ko) | 2009-07-23 | 2013-12-31 | 주식회사 엘지화학 | (메트)아크릴레이트의 효과적인 제조 방법 |
KR101344004B1 (ko) | 2010-04-08 | 2013-12-20 | 주식회사 엘지화학 | (메트)아크릴산 에스테르 제조시 생성되는 부산물의 분해 및 회수방법 |
JP6036400B2 (ja) * | 2013-02-26 | 2016-11-30 | 三菱化学株式会社 | (メタ)アクリル酸エステルの製造方法 |
CN109942424A (zh) * | 2019-04-19 | 2019-06-28 | 泰兴金江化学工业有限公司 | 一种丙烯酸正丁酯重组分回收工艺及装置 |
EP4015498B1 (fr) | 2020-12-18 | 2024-04-24 | Basf Se | Procédé de production continue d'acide acrylique-n-butylester |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2339519A1 (de) * | 1972-08-03 | 1974-02-14 | Celanese Corp | Verfahren zum verestern von acrylsaeure mit alkanol |
DE19547485A1 (de) * | 1995-12-19 | 1996-05-09 | Basf Ag | Verfahren zum Verestern von (Meth)acrylsäure mit einem Alkanol |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB923595A (en) * | 1960-12-03 | 1963-04-18 | Distillers Co Yeast Ltd | Improvements in and relating to the production of acrylic esters |
DE1949434C3 (de) * | 1969-09-30 | 1973-09-20 | Sumitomo Chemical Co., Ltd., Osaka (Japan) | Verfahren zur Gewinnung von Methyl methacrylat |
JPS5762229A (en) * | 1980-10-02 | 1982-04-15 | Mitsubishi Petrochem Co Ltd | Recovery of useful component from heavy substance obtained as by-product in preparation of acrylic ester |
CN1058390A (zh) * | 1990-07-13 | 1992-02-05 | 梁效成 | 含烷氧基丙酸酯废液的处理方法 |
JPH0768168B2 (ja) * | 1991-07-12 | 1995-07-26 | 東亞合成株式会社 | アクリル酸エステルのミカエル付加物の分解方法 |
CN1026104C (zh) * | 1992-03-17 | 1994-10-05 | 侯玉里 | 丙烯酸酯类废油再生工艺 |
JP2943523B2 (ja) * | 1992-08-12 | 1999-08-30 | 東亞合成株式会社 | アクリル酸エステルのミカエル付加物から有用化合物を製造する方法 |
-
1995
- 1995-09-28 DE DE19536191A patent/DE19536191A1/de not_active Withdrawn
-
1996
- 1996-08-23 US US08/701,989 patent/US5910603A/en not_active Expired - Lifetime
- 1996-08-26 CA CA002184197A patent/CA2184197A1/fr not_active Abandoned
- 1996-08-30 TW TW085110598A patent/TW472039B/zh not_active IP Right Cessation
- 1996-09-04 MY MYPI96003665A patent/MY115846A/en unknown
- 1996-09-12 MX MX9604041A patent/MX9604041A/es unknown
- 1996-09-16 CZ CZ962701A patent/CZ270196A3/cs unknown
- 1996-09-25 CN CN96113380A patent/CN1084325C/zh not_active Expired - Lifetime
- 1996-09-25 KR KR1019960042408A patent/KR100441360B1/ko not_active IP Right Cessation
- 1996-09-26 DE DE59606299T patent/DE59606299D1/de not_active Expired - Lifetime
- 1996-09-26 EP EP96115453A patent/EP0767163B1/fr not_active Expired - Lifetime
- 1996-09-27 SG SG9610698A patent/SG83651A1/en unknown
- 1996-09-27 JP JP8256717A patent/JPH09110791A/ja not_active Withdrawn
-
2007
- 2007-02-02 JP JP2007024607A patent/JP4384185B2/ja not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2339519A1 (de) * | 1972-08-03 | 1974-02-14 | Celanese Corp | Verfahren zum verestern von acrylsaeure mit alkanol |
DE19547485A1 (de) * | 1995-12-19 | 1996-05-09 | Basf Ag | Verfahren zum Verestern von (Meth)acrylsäure mit einem Alkanol |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6512138B1 (en) | 1999-05-18 | 2003-01-28 | Basf Aktiengesellschaft | Preparation of (meth)acrylates |
Also Published As
Publication number | Publication date |
---|---|
EP0767163B1 (fr) | 2001-01-10 |
TW472039B (en) | 2002-01-11 |
CN1150586A (zh) | 1997-05-28 |
JP4384185B2 (ja) | 2009-12-16 |
MY115846A (en) | 2003-09-30 |
DE59606299D1 (de) | 2001-02-15 |
KR970015556A (ko) | 1997-04-28 |
DE19536191A1 (de) | 1997-04-03 |
JP2007145857A (ja) | 2007-06-14 |
KR100441360B1 (ko) | 2004-10-08 |
CA2184197A1 (fr) | 1997-03-29 |
MX9604041A (es) | 1997-03-29 |
CZ270196A3 (en) | 1997-06-11 |
JPH09110791A (ja) | 1997-04-28 |
CN1084325C (zh) | 2002-05-08 |
US5910603A (en) | 1999-06-08 |
SG83651A1 (en) | 2001-10-16 |
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